Treatment of hydrocarbons



june i9, i934. A. FISHER ET AL TREATMENT OF HYDROCARBONS Filed Dc.

Patented June'v v.

UNI'raafs'TA'rr:'

TREATMENT F HYDROCRBON S Alfred Fisher and Gustav `Eglofl, Chicago, lll.,

assignors to,Universal Oil Products Company,

Chicago, Ill.,

a corporation of South Dakota This invention relates to the treatment of liquid and solid hydrocarbonaceous materials and more particularly refers to an improved process and apparatus for the conversion an'd coking of a mixture of hydrocarbon oil and solid bituminous or hydrocarbonaceous material accompanied by substantial devolatilization of the carbonaceous residue.

Suitable charging stocks for the process of the present invention comprises any hydrocarbon oil ranging from relatively light distillates such .als gasoline, kerosene, naphthas, etc. to heavy residual pils, asphalts, pitches and the like-containing appreciable quantities of solid bituminous or hydrocarbonaceous materi-al which has been added thereto orl which the oil contains` in ,its natural' state. When Vsolid hydrocarbonaceous material such as coal'or coal wastes, peat, lignite,

natural or synthetic asphaltic materials and the like are added to the oil they are preferably added in pulverized or colloidal form in such amanner and in such quantities that no objectionable amount of solid material will separate from the mixture and be deposited during passage there2 of through the heating element, through which the charging stock is fed prior to its introduc-v tion'into the coking zone.

0 products, such as motor fuel,of high antil-:nockl The process is preferably operated for the production of maximum yields of light distillate value, togetherwith the production ofv a carbonaceous residual product of low volatile con- Atent. However, when desired, the process may be operated for the production of high yields of gas at the expense or even to the exclusion of light distillate products.

Theprimary principles of the present invention comprise'subjecting charging stock, comf prising liquid and solid hydrocarbonaceous material, and intermediate liquidl products of theoperation to conversion and coking, periodically isolating the coke thus produced from the cracking and coking cycle and subjecting it to devolatilization by passing therethrough distillate produced by the cracking and coking operation reheated to a relativelyhigh temperature. l

A more specific embodiment of ,the invention may comprise subjecting charging stock comprising a mixture fhydrocarbon oil and coal to heating in a heating element, introducing the heated materials into an enlarged coking zone,

subjecting vapors from the coking zone to fractionation, condensing and collecting a relatively lightdistillate product resulting from said fractionation, subjectingv reflux condensate resulting from said fractionation to independently controlled conversion conditions in a separate heating element and introducing the heated material into said coking zone, periodically isolating said coking zone from the operating cycle described and accomplishing conversion and coking of the charging stock and reiiux condensate in an alternate cokingzone, heating said relatively light distillate product resulting from the conversion and coking operation to a relatively high temperature in a separate heating element, introducing the heated material into the bed of coke in said isolated coling zone, separately fractionating the vapors therefrom and separately condensing and collecting the light distillate product.

The heating element through which the charging stock is passed, prior to its introduction into the coking zone, may employ relatively mild conversion conditions, or temperatures below the conversion range may be utilized in this zone. In any event ythe conditions employed in this zone preferably are sulliciently mild topreclude the deposition of anyobjectionable.quantity of solid materail in the heating element.

When the process /is operated for the production of maximum yields of light distillate products, such as motor fuel `o1 high antiknock value, temperature and pressure conditions emp'loyed in the heating element through which distillate from the cracking and coking operation is passed are, preferably, not sufliciently severe to eiect the production of undesirable quantities of g'as and in the preferred embodiment of thefinvention are of a nature which will ellect conversionof reforming of the distillate for the production of maximum yields of material of motor fuel boiling range having high antiknock characteristics. However, when the production of high yieldsl of gas is desired more severe conversion conditions may -be employed in this zone nd in all cases the heated distillate is introduced intol the bed of coke at a temperature suf-A lcient to effect substantial .devolatilization there- Reflux condensate produced by fractionation of the vapors evolved in the devolatilizing operation vmay be returned to any or in part, to all the three heatingelements of. 4the system or 'may be withdrawn,l all or in part, 'from the system, Distillate resulting from the devolatilzing operation comprises .the nal light distillate product of the system when such'is produced but may,when desired, and especially when the process is 'operated for the production of high 1 PATENT" OFFICE yields of gas, be returned to' the lheating .element to which distillate from the conversion and A. coking operation is supplied.

. lines 10 and 11 and valve lecting in the lower portion tem through line 27 and valve 28.

' valve 30 to pump The attachedv diagrammatic drawing illusvtrates one specific form of apparatus embodying the princip es of the present invention and the following description of the drawing will serve to more clearly illustrate the process of the invention as it may be practiced in the `apparatus shown.Y Y

Charging stock for the system may be supplied through line 1 and valve 2 to pump 3 from which it is fed through line 4 and valve 5 to heating element 6. Heating element 6 is located in a furnace 7 of any suitable form and the material supplied thereto is heated to the desired ternperature under anydesired pressure Aconditions and passes therefrom through line 8, valve 9,

12 into chamber 1 3.

y Vapors Vfrom chamber 13 pass through lines 14 and 15 and through valve 16 to'fractionation in fractionator 17 wherein the relatively heavy components arecondensed as reflux condensate, colof the'fractonator to be-withdrawn therefrom to further treatment as will belater more fully described. Vapors from fractionator 17, comprising relatively light distillate and uncondensable gas, are withdrawn from the fractionator through line 18 and valve 19 to be subjected to condensation and cooling in condenser 20. the resulting distillate and uncondensable gas from which passes through line 21 and 3valve 22 to be collected in receiver 23.- Gas maybe released from receiver 23 through line 24 and valve 25 while distillate is withdrawn from this zone through line 26 to be subjected, all or in part, to further treatment, as will be later more fully described, or, when desired. a portion of the distillate may be withdrawn from the sysy Reflux condensate collecting within the ylower portion offractionator 17, as already described, is withdrawnv therefrom through line 29 and 31, by meansr of which it i's fed through line 32 and valve 33 to heating element 34. Heating element 34 is located in a furnace 35 of any suitable form and theoil supplied thereto is subjected to conversion under independentlyv controlled'temperature and pressure conditions, which are'preferably more severe than the conditions employed in heating element'6. ,Heated products from heating element 34 pass through line 36 and valve 37 into line 10, commingling therein with the heated charging stock/[from heating element 6 and passing therewith through line 11 and valve 412 into chamber 13.

Chambers 13 and 13 comprisealternatelybperated coking and carbonizing zones, two or more 0f which may be utilized in the operation of the process; For .example when chamber 13 has become filled to the desired extent with coke, re'- sulting 'from the conversion and coking operation, it is. isolated from the conversion and coking portion of the system by closing valves 12 and .16, in lines 11 and 15 respectively; the heated materials from heating elements 6 and 34 being thence passed through line 11' and valve12' into coking chamber 13'. Vapors from chamber 13' thence pass through line`14' and valve 16' into line 15 to be subjected thereafter to the treatment already described.

thel continuityv of the cracking and coking operation is maintained while the cokepreviously deposited in chamber 13 is subjected to devolatilization, as will be debeen lled to the desired extent with coke,

ing, coking and carbonizing operations may be l v`holder or elsewhere, as desire to which vapors from chamber 13 have been subjected. Thus scribed. 1t win be understood that any number.

of a plurality of coking and carbonizing zones may be utilized, forA example, one or more such zones may be utilizedfor the cracking and coking operation while the coke deposited in one or more previously 'volatilized andanother or other such zones are being cleaned and prepared for the coking operation. Thus, after one or more chambers has crackcarried on simultaneously for an indefinite period.

coking cycle, distillate withdrawn from receiver 23 through line 26, as previously described, is supplied through valve 38 to pump 39 from which it is fed through line 40 and valve 41 to heating element 42. Heating element42 is located in a furnace 43 of any suitable form and the distillate supplied thereto is heated to av relatively high temperature under any desired pressure condi- -tions and is thence discharged, preferably without substantial loss of heat, through line 44, line .45and valve 46 into-the bed of coke in chamber 13 preferably being introduced into the lower portion of this zone in such a'manne'r as to pass upward through substantially the entire mass of coke therein'. whereby substantial devolatilization of the coke is accomplished. Vapors resulting from the devolatilizing or carbonizing operation pa-ss from chamber 13. through line 14, line 47 and valve A48 to` fractionation in fractionator '49. It will be understood that when chamber 13' is being utilized as the carbonizing zone the heated distillate from heating element 42 passes fromline 44 through line into coking cham er 13' .and

47 a d valve 48' into line 47`and thence to fractona or 49.

operated zones is being de-Y After a substantial deposit of coke has been accumulated inchamber 13for example, and ,this zone has been isolated from the cracking .and

The function of fractie-hater 49 will dpend primarily upon the desired products for which the process is operated. When maximum quantities of light distillate such'as motor fuelof high antiknock value are desired, fractionator 49 may function in much the same manner as fractionator 17, distillate and uncondensable gas being withdrawn through line .50 and valve 5l, subjected to condensation and cooling in condenser 52 thereafter passingA through 4line 53 and valve 54 tu be collected in receiver 55, fromwhich uncondensable gas may be released through line 56 and'valve 57 while distillate is withdrawn through line 58 and valve 59. However, when the process is op rated for the production of high yields of gas to the exclusion of light distillate products, fractionation may be so controlled in column 49 that'substantiallyl onl uncondensable gas is withdrawn from thc upper portion thereof. passing through line 60 and v lve 61 to a gas ca'se column 49, mayl if desir function as an absorber, absorber oil being 'ntroduced through line 62 and valve 63 while the enriched absorber oiliswithdrawn from the lower portion of column 49 through line 64 and valve 65. When the liquid portion of'. the charging stock supplied to the process is of such a nature that it 'will function as a. suitable absorber oil. all or a portion of it maybe introduced into column 49, as described, in which case the enriched absorber oil is preferably directed to heating element 6 by well known In the latter the reux condensate may be treated in any combination of the manners described.

Pressures employed within the system may Vrange from substantially atmospheric to superatmospheric pressures as high as 2000 pounds, ori-more, per sq. in. Temperatures employed in the various'heating elements may range from temperatures below the conversion range, `of the order to 750 F. or less to gas-makingftemperatures of the order of 1800 F. or thereabouts. Temperatures employed in the heating element to which the charging stock is suppliedl may range from 750 F. or less to 900 F. or there- 'abouts Substantial super-atmospheric pressures of the order of 100 to 500 pounds per sq. in. are preferably employed in this zone. The heating element to which reflux condensate from the fractionator of the conversion and coking system is supplied preferably utilizes temperatures of the order to 900 to v1050t F. with pressures ranging from 100 to 500 pounds or thereabouts per sq. in. Pressures emplcyedin the chamber or chambers utilized as a reaction and coking zone preferablyV range from 100 to 500 pounds or thereabouts per sq. in. although lower pressures down to substantially atmospheric may be employed, when desired. Carbonization of 'the coked residue is preferably effected at substantially atmospheric or relativelyv low super-atmospheric pressure a1- though, when desired, substantial super-atmospheric pressure up to 500 pounds or thereabouts per sq. in. may be employed in the vcarbonizing Zone. When conversior. or reforming of thedistillate form the cracking. and coking operation for the production of maximum yields of high antiknock motor fuel is desired` this materiaLwhich serves as a heat carrying medium for the carbon izing operation, is preferably subjected, in the heating element, to temperatures of the order of 950 to 1050 F. under substantial super-atmospheric pressures ranging from 300 to 800 pounds orl more per sq. in. When high yields of gas are desired the distillate maybe subjected to higher temperaturesh ranging, or example, yfrom 1000 to 1800 F. preferably under'substanl tially atmospheric'or relatively low super-atmospheric pressure. l

As a specific example of the operation of the process of the present invention, th'e charging stock comprises a mixture of about equal parts by weight of mid-continent fuel oil of about 24 l A. P. I. gravity and pulverized bituminous coal having a'volatile content of approximately 38 percent. The coal-in-oilmixture is`subjected in. `a heating element vto a temperature of approximately 800 F. under a super-atmospheric pressure ,of approximately 200pounds per sq. in. Reiiux condensate from the fractionator of the conversion and coking portion of the system is subjected, in a vseparate heating element, to a temperature of about 950 F. under a super-atmospheric pressure of approximately 350 pounds per sq. in.` The coking Vgone is operated under a pressure of approximately 200 pounds per sq. in.,

which pressure is substantially equalized in the succeeding fractionating, condensing and collecting portions of thenconversionand'coking system. The coke 'produced' during this portion of the operation may have a volatile 'contentof approximately 15 percent and the distillate pro-- duced which may, for example, have an end boiling point of approximately 500- F.,-i'nay have anantiknock value equivalent to an octane number 'of approximately 50. This portion of the operation may yield, per barrel of lcharging stock, approximately 170 pounds of coke, about 55 percent of light distillate and approximately 600 cubic feet of gas. When the coking zone has become substantiallyfllled with coke it is isolated from' the cracking and coking cycle, which is continued in an alternate coking zone. Distillate produced by the cracking and coking operation heated in a separate heating element to a temperature of approximately 1000 F. under a super-atmospheric pressure o f about 800 pounds per sq. in.,y is thence introduced into the bed of coke in the chamber isolated'from the cracking and coking cycle. The carbonizing zone'is maintained under be reduced to less than 5 percent and the antiknock value of the distillate may be increased to an octane number of approximately' '78.' The motor fuel of improved antiknock value thus recoveredmay be equivalent to approximately 82 percent of the distillate subjected to retreatment.v

It will be understood that the foregoing ex- .ample illustrates only one of the many types of operation possible within the concepts of the present invention and shouldV therefore not be construed asa limitation. p l Weclaim as our invention: f

1. A process for producing anti-knock motor fuel and coke which comprises subjecting a mixture ,of hydrocarbon oil and solid carbon'aceous materialv to cracking conditions of temperaturev and.pressure,'separating the mixture into vapors and a mass of coke containing volatiles, fractionating the vapors to forni heating a portion of the gasoline to a temperature adequate to vaporizebvolatiles contained inthe coke, and then passing the thus heated gasoline through said mass of coke.

2. In a process for the "conversion of hydrocarbon oils and solid y,carbonaceous materials wherein a mixture of said materials is continuously subjected to conversion` conditions in a heating coil and thenceintroduced into an enlarged raction zone wherein coke containing volatiles deposits and from whichf vapors are withdrawn to' subsequent fractionation'to condense the products heavier than motor fuel distillate and the Afinal vapors condensed and the motor fuel like distillate recovered, the improvement which comprises isolating said reaction zone from the system when a substantial body of said coke has deposited therein While continuing the `discharge of said mixture from the heating coil a gasoline distillate,.-I

subjecting'the same;to con ing the resulting products.

k3. The process as characterized in tha -by .said vfracti mation is pass .heating coil maintained at than the first-mentioned, heating co yit dened by claim t reflux condensate formed ed through asecond higher temperature discharged into the first-mentioned. reaction zone during the discharge of the heated mixture from densationl and collect- 2 further i1 and then the rst-mentione zone.

dheating coil into this reaction ALFRED FISHER. GUSTAV EGLOFF.

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